Organometallics
Communication
(5) For Ru-based catalysts, see: Zeng, G.; Sakaki, S.; Fujita, K.-I.; Sano,
H.; Yamaguchi, R. ACS Catal. 2014, 4, 1010−1020 and references cited
therein.
the 2-hydroxypyridine derivative. Unfortunately a bis-hydrox-
ypyridine complex (7) formed that was catalytically inactive (see
(6) For Rh-based catalysts, see: Zweifel, T.; Naubron, J. V.;
In summary, we have developed a new series of homogeneous
nickel catalysts supported by tris(3,5-dimethylpyrazolyl)borate
and 2-hydroxyquinoline ligands for the acceptorless dehydrogen-
ation of a variety of alcohols to afford ketones, esters, and
lactones. The same nickel catalysts are also capable of
hydrogenating aldehydes and ketone moieties with a moderately
high hydrogen pressure. Therefore, these complexes represent a
rare class of catalyst for the acceptorless, reversible dehydrogen-
ation/hydrogenation of alcohols. Our experimental results
suggest that a stepwise pathway, involving a β-hydride
elimination from the related nickel alkoxide species, is less likely
to occur in this system. Control experiments with different Tp′Ni
precursors demonstrated the role of the 2-hydroxyquinoline
ligand in the dehydrogenation reaction.
Grutzmacher, H. Angew. Chem., Int. Ed. 2009, 48, 559−563 and
̈
references cited therein.
(7) For Ir-based catalysts, see: Mena, I.; Casado, M. A.; Polo, V.;
Garcia-Orduna, P.; Lahoz, F. J.; Oro, L. A. Angew. Chem., Int. Ed. 2012,
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(8) For Os-based catalysts, see: Bertoli, M.; Choualeb, A.; Lough, A. J.;
Moore, B.; Spasyuk, D.; Gusev, D. G. Organometallics 2011, 30, 3479−
3482 and references cited therein.
(9) (a) Zhang, G.; Hanson, S. K. Org. Lett. 2013, 15, 650−653.
(b) Zhang, G.; Vasudevan, K. V.; Scott, B. L.; Hanson, S. K. J. Am. Chem.
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Forster, M.; Bielinski, E. A.; Hazari, N.; Holthausen, M. C.; Jones, W. D.;
̈
Schneider, S. ACS Catal. 2014, 4, 3994−4003. (c) Bonitatibus, P. J., Jr.;
Chakraborty, S.; Doherty, M. D.; Siclovan, O.; Jones, W. D.; Soloveichik,
G. L. Proc. Natl. Acad. Sci. U. S. A. 2015, 112, 1687−1692.
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(e) Zeng, G.; Sakaki, S.; Fujita, K.-I.; Sano, H.; Yamaguchi, R. ACS Catal.
2014, 4, 1010−1020.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental procedures, product characterization data,
and X-ray crystallographic data for 2a−c and 7 (CCDC
(12) (a) Yamaguchi, R.; Ikeda, C.; Takahashi, Y.; Fujita, K.-I. J. Am.
Chem. Soc. 2009, 131, 8410−8412. (b) Fujita, K.-I.; Tanaka, Y.;
Kobayashi, M.; Yamaguchi, R. J. Am. Chem. Soc. 2014, 136, 4829−4832.
(13) Jones, W. D. The Effects of Ancilliary Ligands on Metal-Carbon
Bond Strengths. In Topics in Organometallic Chemistry: C-H Bond
Activation and Catalytic Functionalization; Doucet, H., Dixneuf, P., Eds.;
Springer-Verlag: Berlin, 2015.
(14) Moore, C. M.; Dahl, E. W.; Szymczak, N. K. Curr. Opin. Chem.
Biol. 2015, 25, 9−17.
(15) Wang, W.-H.; Muckerman, J. T.; Fujita, E.; Himeda, Y. New J.
Chem. 2013, 37, 1860−1866.
X-ray crystallographic data for 2a−c and 7 (CIF)
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
(16) Only two other reports have used a homogeneous nickel catalyst
for ketone hydrogenation: (a) Hibino, T.; Makino, K.; Sugiyama, T.;
Hamada, Y. ChemCatChem 2009, 1, 237−240. (b) Flores-Gaspar, A.;
Pinedo-Gonzalez, P.; Crestani, M. G.; Munoz-Hernandez, M.; Morales-
Morales, D.; Warsop, B. A.; Jones, W. D.; Garcia, J. J. J. Mol. Catal. A:
Chem. 2009, 309, 1−11.
ACKNOWLEDGMENTS
■
This work was supported by the NSF under the CCI Center for
Enabling New Technologies through Catalysis (CENTC), CHE-
1205189. P.E.P. thanks the NSF CENTC REU program for the
support. S.C. thanks Professor Ellen M. Matson (University of
Rochester) for suggesting other possible routes to generate the
nickel hydride species.
(17) For the synthesis of [Tp′Ni(μ-OH)]2, see: (a) Hikichi, S.;
Yoshizawa, M.; Sasakura, Y.; Komatsuzaki, H.; Moro-oka, Y.; Akita, M.
Chem. - Eur. J. 2001, 7, 5011−5028. (b) Santana, M. D.; Lopez
García, L.; Perez, J.; Liu, M. Eur. J. Inorg. Chem. 2008, 2008, 4012−4018.
(18) Crabtree, R. H. Chem. Rev. 2012, 112, 1536−1654.
(19) Almeida, M. L. S.; Kocovsky, P.; Backvall, J.-E. J. Org. Chem. 1996,
61, 6587−6590.
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-Banet, L.;
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